Exhaust gas clean up process

• US 4,820,391 A
• Filed: 06/16/1988
• Issued: 04/11/1989
• Est. Priority Date: 06/16/1988
• Status: Expired due to Fees

• Current Assignee: The United States of America As Represented By The Secretary of Agriculture
• Original Assignee: United States Department of Energy
• Inventors: Walker, Richard J.
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): RYSER, DAVID
• Application Number:
  US07/207,562
• Time in Patent Office: 299 Days
• Field of Search: 423/235, 423/242 A, 423/243, 204/182.3, 204/182.4, 204/182.5, 204/149, 204/151, 204/152, 204/153, 204/301
• US Class Current: 204/526
• CPC Class Codes: B01D 53/60 Simultaneously removing sulfur oxides and nitrogen oxides
• CPC Class Codes: B01D 61/44 Ion-selective electrodialysis
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

A method of cleaning an exhaust gas containing particulates, SO₂ and NO_x includes prescrubbing with water to remove HCl and most of the particulates, scrubbing with an aqueous absorbent containing a metal chelate and dissolved sulfite salt to remove NO_x and SO₂, and regenerating the absorbent solution by controlled heating, electrodialysis and carbonate salt addition. The NO_x is removed as N₂ or nitrogen-sulfonate ions and the oxides of sulfur are removed as a vaulable sulfate salt.

Claims

1. A method of regenerating a spent absorbent used in removing NO_x and SO₂ from exhaust gases, said absorbent including sulfite and bisulfite ions and a metal chelate at least partially loaded with NO_x values, said method comprising:

heating and venting the loaded absorbent for at least 4 hours at a temperature of at least 60°

C. to regenerate the metal chelate in respect to NO_x absorption;

depleting sulfite and bisulfite ions from said absorbent in a first compartment of an electrodialysis cell having an anode and cathode, said first compartment defined between a first cation selective membrane disposed towards the cathode and an anion selective membrane disposed toward the anode;

concentrating sulfite and bisulfite ions in an aqueous solution in a second compartment adjacent to said first compartment across said anion selective membrane in the electrodialysis cell, said second compartment defined between said anion selective membrane and a second cation selective membrane towards said anode;

oxidizing a portion of the sulfite concentrated in the second compartment to form a sulfate salt and drying the sulfate salt to a solid for withdrawal;

adding a soluble carbonate to the spent absorbent to convert bisulfite to sulfite ions and thereby regenerate the absorbent in respect to SO₂ absorption;

returning the regenerated absorbent into contact with said exhaust gases.

2. The method of claim 1 wherein said sulfite and bisulfite ions are in aqueous solution with cations selected from the group consisting of alkali metal cations and ammonium cations and wherein said soluble carbonate is selected from the group consisting of alkali metal carbonates and ammonium carbonate.

3. The method of claim 1 wherein said loaded absorbent is heated to a temperature of 60°

-100°

C. and held at this temperature for 4-24 hours with venting to regenerate the metal chelate for NO_x absorption.

4. The method of claim 1 wherein the polarity of the anode and cathode of said electrodialysis cell is periodically reversed and consequently the location of said first and second compartments exchanged to reverse the flow of sulfite and bisulfite ions through the anion selective membrane.

5. The method of claim 4 wherein residual absorbent containing metal chelate following polarity and compartment reversal is collected and returned into contact with the exhaust gases.

6. The method of claim 1 wherein the polarity of the electrodialysis cell is reversed about every 5-100 minutes.

7. The method of claim 1 wherein aqueous solutions of sodium sulfite and sodium bisulfite are concentrated in the second compartment of the electrodialysis cell.

8. The method of claim 1 wherein the concentrated aqueous solution of sulfite and bisulfite ions is treated with alkali to convert bisulfite to sulfite, oxidized to form sulfate and evaporated to dryness for withdrawal of a sulfate salt.

9. The method of claim 1 wherein said metal chelate is a ferrous salt of ethylenediaminetetraacetic acid (EDTA).

10. The method of claim 1 wherein a flow of aqueous metal sulfate solution is circulated between the cathode and the anode of the electrodialysis stack with hydrogen gas generated at said cathode and oxygen gas generated at said anode, said method further including the steps of venting hydrogen gas from said solution prior to contact with said anode and venting oxygen gas from said solution prior to contact with said cathode.

11. A method of cleaning an exhaust gas containing SO_x and NO_x comprising:

scrubbing said exhaust gas with an aqueous absorbent containing a sulfite and a metal chelate, said sulfite acting to take up SO₂ and water to form bisulfite and said metal chelate acting to take up NO_x as the absorbent is loaded,

heating the loaded absorbent to at least 60°

C. for at least 4 hours to regenerate the metal chelate,

passing the aqueous absorbent through a first compartment from which ions are depleted in an electrodialysis stack having a cathode and an anode, said first compartment defined between a cation selective membrane disposed towards the cathode and an anion selective membrane disposed toward the anode,

passing an aqueous solution through a second compartment into which ions are concentrated in said electrodialysis stack adjacent to said first compartment across said anion selective membrane, said second compartment defined between said anion selective membrane and a second cation selective membrane towards said anode,

passing an electrical current between said anode and cathode to transfer sulfite and bisulfite from the first compartment into the second compartment,

adding carbonate to said absorbent to convert bisulfite to sulfite and

returning the aqueous absorbent into scrubbing contact with said exhaust gases.

12. The method of claim 11 wherein said exhaust gas includes particulates and prior to contact with said aqueous absorbent said exchaust gas is contacted in a scrubber with water for removal of particulates and HCl.

13. The method of claim 11 wherein said exhaust gas is contacted with said aqueous absorbent in turbulent flow to remove any residual particulates.

14. The method of claim 11 wherein the pH of said aqueous absorbent in scrubbing contact with said exhaust gas is between 5-9.

15. The method of claim 11 wherein said aqueous solution into which sulfite and bisulfite ions are concentrated is recirculated through said second compartment and wherein a portion of said concentrated solution is withdrawn, treated with alkali solution to convert bisulfite to sulfite, oxidized to convert sulfite to sulfate, evaporated and dried to recover a solid sulfate salt.

16. The method of claim 15 wherein sodium sulfite and bisulfite concentrate solution is processed to recover a solid sodium sulfate salt.

17. The method of claim 11 wherein a solution of sulfate salt is continuously circulated in contact with the anode and the cathode of said electrodialysis cell with hydrogen gas vented from said circulating solution prior to contact with the anode and oxygen gas vented from said circulating solution prior to contact with the cathode.

18. The method of claim 11 wherein the polarity of the electrodes and the locations of the first and second compartments in said electrodialysis stack are reversed about every 5-100 minutes to reverse the flow of current and ions through the membranes in said electrodialysis stack.

19. The method of claim 11 wherein the aqueous absorbent passing through said first compartment and the aqueous solution passing through said second compartment are at about neutral pH.